Infrared (IR) spectroscopy has a long and successful history as an analytical technique and is used extensively (McKelvy et al., 1996; Stuart, 1996). It is mainly a complementary method to X-ray diffraction (XRD) and other methods used to investigate clays and clay minerals. It is an economical, rapid and common technique because a spectrum can be obtained in a few minutes and the instruments are sufficiently inexpensive as to be available in many laboratories. An IR spectrum can serve as a fingerprint for mineral identification, but it can also give unique information about the mineral structure, including the family of minerals to which the specimen belongs and the degree of regularity within the structure, the nature of isomorphic substituents, the distinction of molecular water from constitutional hydroxyl, and the presence of both crystalline and non-crystalline impurities (Farmel, 1979).

Interaction of methylene blue (MB) with reduced charge Li−montmorillonites (RCM) in the aqueous suspensions was investigated using visible absorption spectroscopy. Dye cation agglomeration and protonation at the clay surface depended very sensitively on layer charge density. With increasing layer charge reduction, the content of agglomerates of MB cations decreased in favor of monomers and the protonated form of MB. Lower negative charge density on the clay basal surface induces a greater distance between neighboring MB cations sorbed at the clay surfaces, which suppresses dye agglomeration. Since each form of MB absorbs visible light at a different wavelength, different layer charge densities induce different colors of the resulting clay−dye suspension. Therefore, visible spectra of MB−smectite suspensions may be a simple but extremely sensitive method for the detection of layer charge density of smectites.

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Visible to near-infrared (NIR) reflectance spectra and mid-IR transmittance spectra are presented here for a collection of dioctahedral smectites. Analysis of the structural OH vibrations is performed by comparing the NIR combination and overtone bands with fundamental stretching and bending absorption features in the mid-IR region. Second derivatives are used to determine the actual band centres, which are often shifted slightly by a spectral continuum in the reflectance or transmittance spectra. New bands have been identified near 4170 and 4000 cm–1 in the NIR spectra of nontronite with tetrahedral substitution. A related band is observed near 4100 cm–1 for montmorillonites with substantial tetrahedral and/or octahedral substitution. These bands are correlated with the mid-IR bands near 680 cm–1 for nontronite and near 630 cm–1 for montmorillonite. Comparison of the OH overtone and combination bands with the fundamental stretching and bending vibrations gives consistent results.

The reduction of structural Fe in smectite may be mediated either abiotically by reaction with chemical reducing agents or biotically by reaction with various bacterial species. The effects of abiotic reduction on clay surface chemistry are much better known than the effects of biotic reduction, and differences between them are still in need of investigation. The purpose of the present study was to compare the effects of dithionite (abiotic) and bacteria (biotic) reduction of structural Fe in nontronite on the clay structure as observed by variabletemperature Mössbauer spectroscopy. Biotic reduction was accomplished by incubating Na-saturated Garfield nontronite (sample API 33a) with Shewanella oneidensis strain MR-1 (Fe II /total Fe achieved was ~17 %). Partial abiotic reduction (Fe II /total Fe ~23 %) was achieved using pH-buffered sodium dithionite. The nontronite was also reduced abiotically to Fe II /total Fe ~96 %. Parallel samples were reoxidized by bubbling O 2 gas through the reduced suspensions at room temperature prior to Mössbauer analysis at 77 and 4 K. At 77 K, the reduction treatments all gave spectra composed of doublets for structural Fe II and Fe III in the nontronite. The spectra for reoxidized samples were largely restored to that of the unaltered sample, except for the sample reduced to 96 %. At 4 K, the spectrum for the 96 % reduced sample was highly complex and clearly reflected magnetic order in the sample. When partially reduced, the spectrum also exhibited magnetic order, but the features were completely different depending on whether reduced biotically or abiotically. The biotically reduced sample appeared to contain distinctly separate domains of Fe II and Fe III within the structure, whereas partial abiotic reduction produced a spectrum representative of Fe II -Fe III pairs as the dominant domain type. The 4 K spectra of the partially reduced, fully reoxidized samples were virtually the same as at 77 K, whereas reoxidation of the 96 % reduced sample produced a spectrum consisting of a magnetically ordered sextet with a minor contribution from a Fe II doublet, indicating significant structural alterations compared to the unaltered sample.

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This paper summarizes recent results obtained on chemical modifications of smectites. These include replacement of exchangeable cations with protons, a process connected with smectite autotransformation – attack of protons on the layers and liberation of central atoms from the octahedral and tetrahedral sheets, causing modification of the acid sites on the particles. More severe modifications occur during dissolution in inorganic acids, when the layers are dissolved and threedimensional amorphous silica is formed. The negative charge on the smectite layers can be increased via reduction of structural Fe(III) to Fe(II) or decreased via fixation of small exchangeable cations, such as Li+, upon treatment at elevated temperatures. Heating for 24 h at different temperatures between 100 and 300ºC leads to a series of chemically similar materials of different charge, prepared from the same parent mineral. Such series are suitable for investigation of the effect of the layer charge on selected properties of smectites. Fe(II) can be partly stabilized in reduced smectites by Li fixation upon heating.

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